JPS5968367A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. excellent in mechanical strength, flame retardance, and moldability, by incorporating epoxy resin, flame retardant, and flame-retardant assistant with a blend of polyester and polyphenylene sulfide. CONSTITUTION:5-95pts.wt. thermoplastic polyester (A) (e.g., Novadur 5008 made by Mitubishi Chemical Co.), 95-5pts.wt. polyphenylene sulfide (B) (e.g., Ryton V-1 made by Phillips Petroleum Co.), with the proviso that the total amt. of A and B is 100pts.wt., 0.1-20pts.wt. epoxy resin (novolac types being pref.), 0.1-50pts.wt. flame retardant having an onset temp. of wt. loss by thermogravimetry of 260 deg.C or higher (e.g., decabromodiphenyl ether), and 0.1-20pts.wt. flame-retardant assistant (e.g., antimony trioxide) are incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent compatibility and flame retardancy.

Thermoplastic polyester groups (hereinafter abbreviated as polyester) represented by polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)
and polyphenylene sulfide (hereinafter abbreviated as 1pps)
has excellent heat resistance and chemical resistance, and is used in a variety of applications as engineering plastics, but each resin needs to be improved in order to be used in a wider range of applications.

A blend of polyester and PPS has been studied as a yarn that complements each other's shortcomings, such as the heat resistance, hydrolysis resistance, and flame retardance of the former, and the impact resistance and colorability of the latter, but As a result, the mechanical strength was greatly reduced, and flame retardancy and workability during molding were also problematic, so it was not of commercial interest.

As a result of intensive studies, the present inventors found that polyester and PP
The present inventors have discovered that a composition prepared by distributing an epoxy resin, a specific flame retardant/I, and a flame retardant aid to S has excellent mechanical strength, flame retardancy, and workability during molding processing, and has arrived at the present invention. .

That is, the present invention provides +Al polyester 5~c>sit
part, (BIPP895~5M Tairabe, (for a total of 100 L Yaribe with Cl epoxy resin (capital and f) 11) 0.1
~ 20 folds, 3 (i' fold reduction start degree (5% stone reduction point) h'' - 260C or higher ((A) and (Bl)
0.1 to 50 parts by weight (per 100 parts by weight in total) and 0.1 to 20 parts by weight (per 100 parts by weight in total of (A) and (Bl)) and flame retardant aid The polyester used in the present invention to provide a flame-retardant Vμ resin composition includes terephthalic acid,
Isophthalic acid, orophthalic acid, naphthalene dicarboxylic acid.

4.4'-diphenyldicarboxylic acid, diphenyl ether dicarboxylic acid, (χ, β-bis(4-carboxyphenoxy)ethane, adipic acid, sepacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid) dicarboxylic acid or its ester forming visiting conductor and ethylene glycol, etc.
Propylene glycol, phthanediol, bentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexane dimetatool, hydroquinone, bisphenol A, 2.2
- Polyester obtained from glycols such as bis(4'-hydroxyethoxyphenyl), xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends. 1 Usually, the intrinsic viscosity [η] measured at 30C in a mixed solvent of phenol and tetrachloroethane with an N ratio of 6:4 is 0~1.
．． A range of 5 dl/l is used.

In addition, as a comonomer component, hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, lactone compounds such as propiolactone, butyrolactone, valerolactone, 5-caprolactone, or thermoplasticity are retained. Polyfunctional ester-forming groups such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid may be included within the range.

Also, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, dichloroterephthalic acid, 5-tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, 7-
A thermoplastic polyester copolymerized with a no-ronone compound having an aromatic nucleus such as an ethylene oxide adduct of trabromobisphenol A and a halogenated moiety such as chlorine or bromine as a substituent and an ester-forming group. Also includes resin.

Particularly preferred polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly(ethylene butylene terephthalate), poly(cyclohexane dimethylene terephthalate), poly(butylene tetramethylene prephthalate), 2.2- Examples include bis(β-hydroxyethoxytetrabromophenyl)furopane and polybutylene terephthalate.

It is preferable that the amount of the 41q unit contained in the composition is 70 mol % or more, and if the amount is less than 70 mol %, it is difficult to obtain a composition with the first characteristics.

A method of reacting sodium sulfide with p-dichlorobenzene is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add an alkali hydroxide. Copolymerization component R It is acceptable if the copolymerization component contains a tro group, a phenyl group, an alkoxy group, a carboxylic acid group, etc. as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 1.
It is preferably 0 mol% or less. Especially phenyl and biphenyl having trifunctionality or more.

When a naphthyl sulfide bond or the like is selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

Such PPS can be produced by common manufacturing methods, such as reaction of +11 halogen-substituted aromatic compound with a polymerized alkali (see U.S. Pat. ) (2) Condensation reaction of thiophenols in the coexistence of an alkali catalyst or copper salt (US Patent No. 6,274,165, British Patent No. 116)
(Refer to No. 0660) (3) Condensation reaction of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst
255, Belgian special ¥'fi 29437 sanfuku), etc.

PPS is currently available on the market as Rydon PPS from Phillips Petroleum Company. Rydon PPs has v-1, P-2, P depending on its crosslink density and viscosity.
There are grades -3, P-4, and R-6. When combined with polyester, Rydon V-1 has a low degree of crosslinking, but the viscosity is too low, and Rydon R-5 and P-4 have a high viscosity, but the degree of crosslinking is too high, resulting in good compatibility. cannot be obtained, but it can be used by using epoxy resin together.

In the present invention, it is believed that the epoxy resin is effective in reacting with PPS to make it into a polymer, and also reacts with polyester. Therefore, the oxidative crosslinking step, which could not be used conventionally due to its low viscosity, is omitted, and PPS, which has a low degree of coloring, is preferably used. The degree of crosslinking of PPS can be expressed by the relationship between the melt viscosity of the polymer and the non-Newtonian coefficient (Nl). Generally, the larger N is, the higher the degree of crosslinking is.
PS plots the respective logarithms of shear rate and shear stress obtained at a constant time in Viscosity Crushing 11, and defines the slope of the tangent at the point of shear rate 200 (17 seconds) at 300C as the non-Newtonian coefficient N. is 08 and 1.33
It is particularly preferred that the viscosity is between +0.000047X (melt viscosity).

Furthermore, in the present invention, high molecular weight -pps with a low degree of crosslinking, which is known from JP-A-50-84698 and JP-A-51-144495, can also be suitably used.

The epoxy resin used in the present invention has 1 epoxy group.
It can be used to break down one or more pieces, and it can be liquid or solid. For example, bisphenol A, resorcinol, hydroquinone, hylocadecol, bisphenol F% saligenin, 1,3.5-4-lyhydroxybenzene, bisphenol S, trihydroquine-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 1,5-dihydroquine. Naphthalene, cashew phenol, dihydroxy-diphenyl sulfone% 2,2,
5. Glycidyl ethers of bisphenols such as 5-f trakis(4-hydroxyphenyl)hexane, glycidyl ethers such as diglycidyl ether of halogenated bisphenol butanediol instead of bisphenol, glycidyl esters such as phthalomomi glycidyl ester, N - Glycidyl epoxy resins such as glycidyl amine series such as glycidylaniline, linear series such as epoxidized polyolefins, epoxidized soybean oil, etc., and cyclic non-glycidyl epoxies such as vinyl cyclohexene dioxide, dicyclopentadiene dioxide, etc. An example is resin.

A particularly preferred epoxy resin in the present invention is a novolak epoxy resin. Novolac epoxy #-, 1li
(ii) A novolac type phenol resin having two or more epoxy groups is obtained by reacting epichlorohydrin.Novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. The phenols used as this raw material are not particularly limited, but phenol, 0-cresol, m-cresol% p-cresol, bisphenol A, resorcinol% p-tert-butylphenol, bisphenol F, bisphenol S, and mixtures thereof are particularly preferred. used.

Furthermore, epoxidized poly-P-vinylphenol and halogenated versions of these epoxy resins can also be used in the same manner as the novolac type epoxy resin. These epoxy resins may be used individually and/or as a mixture of two or more resins.

The amount of epoxy resin added is P plastic polyester and PPs
The mixture is 0.1 to 20 parts vertically or 05 to 15 parts per 100 parts vertically. The preferred amount of epoxy resin to be added varies depending on the molecular weight of PPS and the intended use, and generally a relatively large amount of epoxy resin is required for low molecular weight 1 pps or extrusion molding compositions requiring high viscosity. If the amount is less than 0.1 parts, the effect will be small, and if it exceeds 20 parts, the mechanical properties may be lost, and depending on the epoxy resin added, bleeding to the surface of the molded product or composition may be affected. This is not preferable because it may significantly reduce the melt flow stability of the product.

Generally, epoxy resins are molded by blending curing agents such as amines, acid anhydrides, multivalued products, and phenolic resins, but in the present invention, no curing agents are used at all, or even if they are used, their activity is It is desirable that the amount of hydrogen be at a molar ratio of half or less of that of the epoxy group component. If a hardening agent used in regular sewing is used in combination, not only will the reaction between the epoxy resin and PPS be inhibited, but the ratio between the epoxy resin and the hardening agent will be inversely
This is because a stable increase in melt viscosity, such as the formation of a crosslinked network, cannot be expected. In the present invention, the effect of using a small amount of curing agent in combination is expected to be to prevent deterioration of bleedability and thermal properties due to addition of epoxy resin.

There are no particular limitations on the structure and chemical composition of the flame retardant used in the present invention, but under the condition of a temperature increase rate of 10 C/min in air, the vorticity at which the heat sink starts to decrease is 26 DC (point of 5% vehicle needle decrease).
It is necessary that it is at least 280U, and preferably it is at least 280U. If the temperature at which IP deterioration starts is below 26 (JC), phenomena such as decomposition and sublimation may occur during molding processes such as pellet production and injection molding, which is a problem.
Specific ■ (as, decabromodiphenyl ether,
2-hydroxyethyl ether of thecabrom biphenyltetrabromo bisphenol A, polycondensate of 2,4.6-dribromophenol, ethylene bis-tetrafuromophthalimide, putrabromo bisphenol A & polycarbonate oligomer triviroethic 7 used as raw material
7B (manufactured by Ferro Corporation), 5-brominated polystyrene, and the like.

these! The amount of l#P agent added can be determined by taking into account the composition ratio of polyester and PPS and the required twist resistance.
It is necessary that the amount is 01 to 50 parts by weight based on the total ID0ffi parts of both resins. If it is less than this, the pheasant pestle will be insufficient and will not achieve the UL standard V-O5v-1.
Moreover, if it exceeds 50 weight #g, the W strength decreases, causing a problem.

It is necessary that the S flame agent used in the present invention be present together with a flame retardant aid consisting of a metal oxide. Specific examples of flame retardant aids include antimony dioxide, antimony pentoxide, antimony disulfide, antimony tribase, antimony pentachloride, antimony tribromide, antimony pentabromide, barium metaborate, lead borate, and aluminum hydroxide. , zirconium oxide, molybdenum oxide, etc., and antimony trioxide is particularly suitable. Also, the total amount of polyester and PPS is 1υo * 0.1 to tyt.
It is necessary that the amount of oil be 20 parts.

The composition of the present invention is a fibrous reinforcing agent such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, spliced fiber, silicon nitride, barium chain acid,
Calcium, carrion, clay, parrophyllite, bentonite, sericite, zeolite, mica,
Mica, nephelinsinite, talc, atalbulgite, wollastonite, processed mineral fiber (PMF), ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide , iron oxide, molybdenum disulfide, graphite, gypsum, glass powder,
Inorganic fillers such as glass beads, glass balloons, quartz and quartz glass, and organic reinforcing fillers such as aramid fibers can be contained in the composition up to 80 M%. When adding these reinforcing agents or fillers, known silane coupling agents can be used. Furthermore, lubricants such as fluororesins and molybdenum compounds can also be used.

In addition, the composition of the present invention may contain a small amount of a mold release agent, a coloring agent, a heat stabilizer, and an ultraviolet stabilizer without departing from the purpose of the present invention.

A foaming agent and a rust preventive agent can be added. Additionally, the non-exploited fIA compositions can also be used in combination with polymers such as F.

Examples of polymers include ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, tl-methylstyrene, vinyl acetate, vinyl chloride, acrylic ester, methacrylic ester, and (meth)acrylonitrile. homopolymers or copolymers of polymers, polyurethanes, polyamides, polyesters, polycarbonates, polyacetals, polysulfones, polyarylsulfones, polyethersulfones, polyarylates, polyphenyls/oxides, polyphenylene ethers, polyetheretherketones 5 polyimides , polyamideimide, silicone ipHL phenoxy resin, fluororesin, polyaryl ether and other grass polymers, copolymers, block and graft copolymers.

The composition of the invention can be prepared by various known methods.

For example, there is a method in which raw materials are uniformly mixed in advance in a mixer such as a tumbler or Henschel mixer, fed into a single-screw or twin-screw extruder, and then melt-kneaded in a bath at 230 to 400 c to prepare pellets. It is also preferable to divide the epoxy resin into two or more times during extrusion kneading and perform five extrusion edges two or more times in order to promote the reaction between PPS and the epoxy resin. It is also possible to melt and knead PPS and novolac type epoxy resin in a dry blend injection molding machine.

The composition of the present invention can be processed not only by injection molding and compression molding, but also by extrusion molding, blow molding, and foam molding, and can be processed into films, sheets, monofilaments, and fibers.

In particular, it can be suitably used for stabilizing electronic components.

/'/・' / / Evaluation of flammability of the composition in the present invention is subject 9 of the American Underwriters O Laboratories standard.
4 (UL94). Specifically, first,
As a test piece, length 5 × width / 2〃 × thickness / was made by injection molding.
16〃 or /32〃 are prepared and used. Using 1000 BTU of gas mainly composed of methane gas as the fire source, adjust the height of the blue flame without yellow tips to 5/4'' using a burner with an inner diameter of 3/8'' and a length of 4''. Fix the specimen so that its length is vertical, and set it so that the distance between the lower end of the specimen and the upper end of the burner is 6/8.Remove indirect flame from the specimen for 10 seconds, Record the subsequent burning time of the specimen (first burning time). Then, immediately after extinguishing the specimen, ignite the flame again for 10 seconds and record the second burning time after the flame is removed. Also, observe whether the molten part of the specimen falls downward during contact with the flame or during the subsequent combustion time and afterglow time.

Next, Examples and Comparative Examples will be given to explain the present invention in detail. In addition, the mechanical properties in the examples were determined to be 6 (11) according to ASTM standards.

Example-1 PBT (Novadour 500 B, manufactured by Mitsubishi Kasei ■)s
o, H part, PPS (Rydon vi, manufactured by Phillips Petroleum Company) 50. *, N part, epoxy resin (Epicron N-695-Dainippon Ink Chemical Co., Ltd. (prepared) 5
1 part, FIRE MAS1'ER as a flame retardant, ■
TSA [Velsieol Corp, (US) Br
Junior 65% weight loss start temperature (5 weight 70 loss)
77 parts by weight of 370C (in air, heating rate 10C15+) and 3 parts by weight of antimony trioxide as a flame retardant additive were uniformly premixed. Next, pellets were obtained by kneading them in a vented extruder (4 (1 m)) heated to 3.00C.The pellets were used to make a cast piece using an injection molding machine. It had excellent bath properties.When the physical properties were measured, the bending strength was 820 K9/
crrL'' and flame retardant T9 (UL-94) old inch was V-0.

Example-2 In Example-1, instead of PBT, the intrinsic viscosity was 1.06.
When a PET flame was used, the appearance of the molded product was good, the bending strength was 850 h/cm", and the flame retardant rating was V- at 5 inches (UL-94).

Met.

Comparative Examples 1 and 2 In Examples 1 and 2, when no flame retardant or flame retardant aid was added, the bending strength was 830 K9A, respectively.
8d OK9/crn'', and the appearance of the molded product was good, but the flammability (UL-94) was judged to be HB, which could extinguish fire even though it did not drip in inches.

Example-6 In Example 1, glass fiber (Glaslon C803MA
411, Asahi Glass■#) When adding 75mt part,
The appearance of the molded product is good, with bending strength of 1850 kg/cmζ tensile strength of 1450 and p/crr? , Izot impact strength (
With notch) 8.5 '-9・rs/cu*, flame retardancy (UL-94) g inch v-0. Example 4 PBT 3011 parts, PPS 70 in implementation flI3
Pyrocheck 77 B [F
Erro Corp, (USA) Br-containing spear 77% by weight, detonation onset temperature (5% loss by weight) 348C] 4! When the molded part was changed to a weight part, the appearance of the molded product was good and the bending strength was 1900.
K9/cm", tensile strength 1480KM bacteria-Izot impact strength (with notch) 9.OK9・(7)/i,
Flame retardancy (TJL-qa) was v-0 at 5 inches.

Comparative Example-6 When the flame retardant and silent combustion additive were not added in Example 4, the molded product had a bending strength of 1880 K9/ctr? ,
Tensile strength: 14 kg/am', Izotsu impact strength: 8
5 and 2・α/i, and the appearance of the molded product was good; however, the appearance of the molded product was good. .

Although it doesn't drip in inches? r' (It was judged as HB without fire.

Comparison fi1-4 Implementation (in qa4, flame retardant tetrabromo bisphenol A [Bjiin 5B8 heavy Tsukuda%, simple reduction start vorticity (5% by weight river loss) was changed to 240C15 mass part, extruder During kneading and injection molding, there was a strong odor of decomposed gas, and the molded product had a dark brown color.Also, the molded product had a bending strength of 1250 k.
P/m", tensile strength 850 h/ca", Izod impact strength (Nottsuchi phrase)4. It had a low value of OK2/27, and was judged to have flame retardancy (UL-1) and old inch V-1.

Comparative Example-5 In Example 4, the flame retardant was hexabromobenzene [Br
Miya - 87 air volume %, Le goods decrease starting temperature (5M volume % loss) 2
When the mixture was partially changed to 50C35, 5-table'4, sublimation was intense during kneading in an extruder and injection molding, and white clouding occurred in the molded product. The molded product has a bending strength of 1500 Kg/cm'
, tensile strength 1100 to 9 pa.

The Izot impact strength (with notches) was as low as 5.5 Kp.-27, and the flame retardant rating was 14 (UL-94) as well as the old inch V-1.

J/'-9 Procedural Amendment ■, Minor Case Indication 1982 Patent Application No. 178625 2, Name of Invention Flame Retardant Resin Composition 3, Relationship with the case of the person making Supplement 11 Patent distributor: 174 3-35-58 Sakato, Itabashi-ku, Tokyo (2
8B) Dainippon Ink and Chemicals Co., Ltd. Representative: Shigeru Kawatoshi f'19 4, Agent: No. 7-20, 11 Motohashi 2, Chuo-ku, Tokyo 103 Details of the invention in the specification in Dainippon Ink and Chemicals Co., Ltd. Contents of Explanation Column 6, Supplement i (2), page 8, lines 13-14 and page 9, line 4, 1 of the same book
"Low viscosity" is revised to "Melt viscosity is low viscosity J".

(3) Same damage, page 8, line 1, to page 9, line 1 [Although good compatibility is not obtained, it can be used by using an epoxy resin together. '' has been revised to ``A good T compatibility could not be obtained.''

f41 Insert the following sentence between the 2nd and 3rd lines of page 10 of the interlude.

"In addition, Juki polyester and P PS 4; l: 41]
From the point of view of properties, it is preferable that the melt viscosity is 11-1 and that there is almost no cross-linking. ”(
5) In the first line of page 19 of the same book, ``Run 1' in the injection molding machine'' was changed to ``Run 1' in the injection molding machine'' to ``Injection molding in the injection molding machine''.

(that's all)

Claims (1)

[Claims] fAJ thermoplastic polyester 5-95 parts by weight, (Bl polyphenylene sulfide 95-5 parts by weight, (based on the total of 100 parts by weight of Cl epoxy resin (France) and (Bl))
01 to 20 parts by weight, a flame retardant with a weight loss start temperature (5% weight loss point) of 260C or higher (based on a total of 100 parts of (A) and (Bl)) and a flame retardant of 0.1 to 50M and a retardant. A flame-retardant resin composition containing 0.1 to 201 parts by weight of a combustion aid (per 10 parts by weight of Al and Bl in total).